Reversible Alkyl-Group Migration between Iron and Sulfur in [Fe₄S₄] Clusters.

ABSTRACT: Synthetic [Fe₄S₄] clusters with Fe-R groups (R = alkyl/benzyl) are shown to release organic radicals on an [Fe₄S₄]³⁺-R/[Fe₄S₄]²⁺ redox couple, the same that has been proposed for a radical-generating intermediate in the superfamily of radical S-adenosyl-l-methionine (SAM) enzymes. In attempts to trap the immediate precursor to radical generation, a species in which the alkyl group has migrated from Fe to S is instead isolated. This S-alkylated cluster is a structurally faithful model of intermediates proposed in a variety of functionally diverse S transferase enzymes and features an "[Fe₄S₄]⁺-like" core that exists as a physical mixture of S = 1/2 and 7/2 s

SUBMITTER: Ye M 

PROVIDER: S-EPMC9526375 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature